JP2919419B2 - Electrolyte for electrolyte - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reacting a nitrogen-containing heterocyclic tertiary amine with a carbonic acid diester to form a corresponding mono- amine.
A nitrogen-containing heterocyclic quaternary ammonium carbonate, which was mixed with an organic acid and decarboxylated to obtain a mono-containing quaternary ammonium carbonate.
It relates to an electrolyte for electrolytic solution comprising a nitrogen heterocyclic quaternary ammonium organic acid salt. [0002] As a method for synthesizing an organic acid salt of quaternary ammonium, generally, a tertiary amine is quaternized with an alkyl halide, dialkyl sulfate or the like under heating, and then a halide anion and a sulfate anion are converted to an organic acid salt. A method of exchanging for an acid is known. For example, when an alkyl halide is used as a quaternizing reagent, the quaternizing reaction is represented by the following formula. R ₃ N + R′X → R ₃ R′N ⁺ X ⁻ (X = halogen) Further, when an anion exchange reaction of a quaternary ammonium halide salt is carried out, Methods for performing anion exchange are known. R ₃ R′N ⁺ X ⁻ + H ⁺ X ⁻ → R ₃ R′N ⁺ A ⁻ where A ⁻ is an anion species to be exchanged. Replace want H ⁺ A ^- in the case of very strong strong acid are biased equilibrium to the right side of the equation, there are cases where it is possible to sufficiently proceed the anion exchange reaction of interest, relatively weak, such as an organic acid With an acid, it is extremely difficult to cause an anion exchange reaction by such a reaction. Other methods include a method of reacting a quaternary ammonium halide salt with an organic acid salt of an alkali metal or an alkaline earth metal, and a method of reacting a quaternary ammonium halide salt with a silver organic acid. In these methods, it is quite difficult to completely remove the starting material anion in the desired quaternary ammonium organic acid salt, which is unsuitable as a production method for obtaining a high-purity quaternary ammonium organic acid salt. . The method using silver organic acid is expensive and unsuitable for industrial production. In view of the above, a method for producing a high-purity quaternary ammonium organic acid salt is as follows:
The most common method is to convert the quaternary ammonium halide salt into quaternary ammonium hydroxide once (reaction a) and then neutralize with an organic acid (reaction b). ## STR3 ## ^{_{R 3 R'N + X - → R}} 3 R'N + OH - ( reaction ^{_{a) R 3 R'N + OH -}} + H + A - → R 3 R'N + A - + H 2 O ( Reaction b) Problems to be Solved by the Invention Various methods are known as a method for producing quaternary ammonium hydroxide by the above-mentioned (reaction a). Expensive. Especially in the production of quaternary ammonium hydroxide as an intermediate of quaternary ammonium organic acid salts, since quaternary ammonium organic acid salts as electrolytes for electrolytes such as batteries and capacitors are extremely unlikely to be mixed with halogen ions. Requires that the halogen ions be controlled on the order of ppm, and the production cost is considerably high. Accordingly, the present invention provides a mono-nitrogen-containing , highly pure and inexpensive
An object of the present invention is to provide an electrolyte for an electrolytic solution comprising a heterocyclic quaternary ammonium organic acid salt. [0008] The electrolyte for the electrolytic solution according to the present invention is a mono-nitrogen-containing heterocyclic quaternary ammonium carbonate obtained by reacting a nitrogen-containing heterocyclic tertiary amine with a carbonic acid diester. characterized in that consisting of nitrogen-containing heterocyclic quaternary ammonium organic acid salt - and then, the mono - mono that generated by the nitrogen-containing heterocyclic quaternary ammonium carbonate is mixed with an organic acid to decarboxylation is there. According to the method for decarboxylating a mono-nitrogen-containing heterocyclic quaternary ammonium carbonate with an organic acid, a high-purity mono-nitrogen-containing heterocyclic quaternary ammonium organic acid salt suitable as an electrolyte for an electrolytic solution is prepared. It can be manufactured at low cost . DETAILED DESCRIPTION OF THE INVENTION nitrogen-containing heterocyclic which is a raw material of the present invention
The ring tertiary amines, nitrogenous heterocyclic amines such as N- methylpyrrolidine, N- ethylpyrrolidine, N-
Methylpiperidine, N-ethylpiperidine, Nn-butylpiperidine, N-methylhexamethyleneimine, N
-Ethylhexamethyleneimine, N-methylmorpholine, N-butylmorpholine, N, N'-dimethylpiperazine, N, N'-diethylpiperazine, 1,5-diazabicyclo [4,3,0] -5-nonene, Nitrogen-containing heterocyclic aliphatic amines such as, 8-diazabicyclo [5,4,0] -7-undecene, pyridine, 4-dimethylaminopyridine, picolines, N-methylimidazole,
N-methylbenzimidazole, quinoline, 4,4'-
Examples thereof include nitrogen-containing heterocyclic aromatic amines such as dipyridyl. Examples of the carbonic ester include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate and the like. The lower the number of carbon atoms in the alkyl group such as dimethyl carbonate, the faster the quaternization reaction proceeds. It can be said that it is a preferable raw material. The anion exchange is completed more quickly as the organic acid is stronger than carbonic acid. In addition, anion exchange is possible even for a weak acid equal to or less than carbonic acid by shifting the equilibrium by removing the carbonate group in the system as carbon dioxide gas. Specific examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, and myristin. Acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, isobutyric acid, isovaleric acid, isocaproic acid, ethylbutyric acid, methylvaleric acid,
Isocaprylic acid, propylvaleric acid, ethylcaproic acid,
Isocapric acid, tuberculostearic acid, pivalic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctane Acid, 2-methyl-2-ethylbutanoic acid, 2-methyl-2-ethylpentanoic acid, 2-methyl-2-ethylhexanoic acid, 2-methyl-2-ethyl-heptanoic acid, 2-methyl-2-propylpentane Acid, 2-methyl-2-propylhexanoic acid,
2-methyl-2-propylheptanoic acid, acrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid,
Dodecenoic acid, tuzunic acid, fisteric acid, goshuic acid, valmitoleic acid, petroserinic acid, oleic acid, elaidic acid, vaccenic acid, cadoleic acid, methacrylic acid, 3-methylcrotonic acid, tiglic acid, methylpentenoic acid, cyclopentanecarboxylic acid Aliphatic monocarboxylic acids such as cyclohexanecarboxylic acid, trifluoroacetic acid, phenylacetic acid, chloroacetic acid, glycolic acid, and lactic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid, hexadecandioic acid, heptadecanoic acid, octadecandioic acid,
Nonadecandioic acid, eicosantioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid, hexylmalonic acid, dimethylmalonic acid, methylethylmalonic acid, diethylmalonic acid, methylpropylmalonic acid, Methylbutylmalonic acid, ethylpropylmalonic acid, dipropylmalonic acid, ethylbutylmalonic acid, propylbutylmalonic acid, dibutylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid 2-methylglutaric acid, 3-methylglutaric acid, 3-methyl-3-ethylglutaric acid, 3,3-diethylglutaric acid, maleic acid,
Citraconic acid, itaconic acid, methylene glutaric acid, monomethyl maleate, 1,5-octanedicarboxylic acid,
5,6-decanedicarboxylic acid, 1,7-decanedicarboxylic acid, 4,6-dimethyl-4-nonene-1,2-dicarboxylic acid, 4,6-dimethyl-1,2-nonanedicarboxylic acid, 1,7 -Dodecanedicarboxylic acid, 5-ethyl-1,
10-decanedicarboxylic acid, 6-methyl-6-dodecene-1,12-dicarboxylic acid, 6-methyl-1,12-dodecanedicarboxylic acid, 6-ethylene-1,12-dodecanedicarboxylic acid, 6-ethyl-1 , 12-Dodecanecarboxylic acid, 7-methyl-7-tetradecene-1,14-dicarboxylic acid, 7-methyl-1,14-tetradecanedicarboxylic acid, 3-hexyl-4-decene-1,2-dicarboxylic acid, 3 -Hexyl-1,2-decanedicarboxylic acid,
6-ethylene-9-hexadecene-1,16-dicarboxylic acid, 6-ethyl-1,16-hexadecanedicarboxylic acid, 6-phenyl-1,12-dodecanedicarboxylic acid,
7,12-dimethyl-7,11-octadecadien-
1,18-dicarboxylic acid, 7,12-dimethyl-1,1
8-octadecanedicarboxylic acid, 6,8-diphenyl-
1,14-tetradecanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2
-Cyclohexanedicarboxylic acid, 4-cyclohexene-
Aliphatic dicarboxylic acids such as 1,2-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, malic acid, glutamic acid and tartaric acid; aliphatic polycarboxylic acids such as citric acid; and benzoic acid and toluic acid , Ethyl benzoic acid, propyl benzoic acid, isopropyl benzoic acid, butyl benzoic acid, isobutyl benzoic acid, sec-butyl benzoic acid, tert-butyl benzoic acid, hydroxybenzoic acid, anisic acid, ethoxy benzoic acid, propoxy benzoic acid, isopropoxy Benzoic acid, butoxybenzoic acid, isobutoxybenzoic acid, secondary butoxybenzoic acid, tertiary butoxybenzoic acid,
Aminobenzoic acid, N-methylaminobenzoic acid, N-ethylaminobenzoic acid, N-propylaminobenzoic acid, N-
Isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid, N-sec-butylaminobenzoic acid, N-tert-butylaminobenzoic acid, N, N
Aromatic monocarboxylic acids such as dimethylaminobenzoic acid, N, N-diethylaminobenzoic acid, nitrobenzoic acid, fluorobenzoic acid and resorcinic acid (including o, m, p-isomers), phthalic acid , Isophthalic acid, terephthalic acid,
Aromatic polycarboxylic acids such as nitrophthalic acid, trimellitic acid, hemmellitic acid, trimesic acid, pyromellitic acid, phenol, p-fluorophenol, β-naphthol, o-nitrophenol, p-nitrophenol, p
-Aminophenol, catechol, resorcin, 2-chlorophenol, 2,4-dichlorophenol, 4,
Phenols such as 4'-dihydroxydiphenyl-2,2-propane can be exemplified. The quaternization reaction is the first step of the nitrogen-containing hetero
The molar ratio of the cyclic tertiary amine to the carbonic acid diester is 0.2 to 0.2
5, more preferably from 0.3 to 3, in the presence or absence of a solvent, at a reaction temperature of from 20 to 200 ° C, more preferably from 3 to 3.
Performed at 0-160 ° C. When the normal nitrogen-containing heterocyclic tertiary amine is sufficiently converted to quaternized, unreacted nitrogen
When the heterocyclic tertiary amine or carbonic acid diester is used in a solvent, the tertiary amine or the carbonic acid diester is distilled off together with the solvent or, if necessary, recrystallized with an appropriate organic solvent and sent to the second step. In the second step, usually, a stoichiometric value or a small excess of an organic acid is added dropwise to a mono-nitrogen-containing heterocyclic quaternary ammonium carbonate in the presence or absence of a solvent, and the generated carbon dioxide gas is added. It is removed under reduced pressure or by blowing an inert gas into the reaction system. At this time, the reaction that takes place is represented by the following formula when dimethyl carbonate is used as a raw material. Embedded image (In the formula, R ₁ R ₂ R ₃ is a hydrocarbon residue of a nitrogen-containing heterocyclic tertiary amine, and Y is a conjugate base of an organic acid.) When a by-product alcohol and a solvent are used after the reaction, Mo solid obtained later evaporation of the solvent is an object of the
No-nitrogen-containing heterocyclic quaternary ammonium organic acid salt.
If necessary, a high-purity product can be obtained by recrystallization or the like using an appropriate solvent. Furthermore, when using small excess organic acid than the stoichiometric value to remove carbonate ions completely, it can be removed by treatment such as recrystallization excess organic acid. The mono-nitrogen-containing heterocyclic quaternary ammonium organic acid salt obtained here is dissolved in a solvent and used as an electrolytic solution. EXAMPLES The method for producing a mono-nitrogen-containing heterocyclic quaternary ammonium organic acid salt used as an electrolyte for an electrolytic solution in the present invention will be described more specifically with reference to the following examples. Reference Example 1 (First step) In a stirred autoclave, 17.8 g of dimethyl carbonate and 20.0 g of triethylamine were used as a solvent to prepare 20.times.
0 g, reaction temperature 115 ° C., reaction pressure 5.0 kg
/ Cm ² G for 12 hours. After the reaction, the autoclave was cooled, and the reaction solution was taken out and analyzed by gas chromatography. The conversion of triethylamine was 94.6%.
The solid yield after distilling off the unreacted substances and the solvent was 34.0 g (89.9% of the theoretical amount). Elemental analysis and H-NMR confirmed that this was triethylmethylammonium methyl carbonate. (Second step) triethylmethylammonium methyl carbonate4.
5 g was dissolved in 10.0 g of water, and maleic acid was added thereto.
When a solution in which 7 g was dissolved in 20.0 g of water was gradually added, carbon dioxide gas was violently generated. Degassing was performed at 40 ° C./20 mmHg for 2 hours to remove carbon dioxide more completely. 20 carbonate ions by ion chromatography
After confirming that the concentration was not more than ppm, water was distilled off. The residue was recrystallized from methyl ethyl ketone to obtain 3.1 g of high-purity mono-triethylmethylammonium malate (84.4% yield based on triethylamine). The resulting mono - was subjected to ion analysis of triethylmethylammonium ^{maleate, Cl -, Br -, SO} 4 2-, NO 3
^- impurities such is less than both 1 ppm, it was confirmed that an extremely high purity salts. Example 1 (First step) In a stirred autoclave, 68.8 g of dimethyl carbonate and N-
65.0 g of methylpyrrolidine and 60.0 g of methanol as a solvent were charged, the reaction temperature was 120 ° C., and the reaction pressure was 3 k.
The reaction was performed at g / cm ² G for 6 hours. After the reaction, the autoclave was cooled, and the reaction solution was taken out and analyzed by gas chromatography. The conversion of N-methylpyrrolidine was 9%.
It was 8.1%. Unreacted materials and the solvent were distilled off, and 130.6 g of a solid was recovered (theoretical amount of 97.6).
%). From elemental analysis and H-NMR, it was confirmed that this solid was N, N-dimethylpyrrolidinium methyl carbonate. (Second step) N, N-dimethylpyrrolidinium methyl carbonate 1
Except that 0.0 g and 8.3 g of adipic acid were used, the same operation as in the second step of Reference Example 1 was carried out to obtain 12.7 g of dimethylpyrrolidinium monoadipate (88.5% yield based on N-methylpyrrolidine). Rate). Example 2 The same procedure as in Example 1 was repeated except that 10.0 g of N, N-dimethylpyrrolidinium methyl carbonate and 5.4 g of phenol were used in the second step of Example 1. 10.7 g of dinium phenolate (N
94.7% yield based on -methylpyrrolidine). Example 3 (First step) 8.8 g of dimethyl carbonate and 10.0 parts of pyridine as raw materials
g, except that 10.0 g of methanol was used as the solvent.
When the same reaction as in Reference Example 1 was performed, 16.8 g of a solid was obtained (78.5% of the theoretical yield). Elemental analysis, HN
From MR and the like, it was confirmed that this solid was N-methylpyridinium methyl carbonate. (Second step) 10.0 g of N-methylpyridinium methyl carbonate
Reference Example 1 (second step) except that acetic acid and 3.1 g of acetic acid were used.
8.7 g of N-methylpyrrolidinium acetate (75.4% yield based on pyridine) was obtained in the same manner as described above. Example 4 The N-methylpyridinium methyl carbonate synthesized in Example 3 (first step) was mixed with an equimolar amount of maleic acid, and N-methylpyridinium was mixed with maleic acid in the same manner as in Example 3 (second step). −
Methylpyridinium malate was synthesized. By recrystallization, the target compound was obtained in a theoretical yield of 96.0% (yield to pyridine: 75.4%). Example 5 (First Step) The same reaction as in Reference Example 1 except that 17.0 g of dimethyl carbonate and 10.0 g of 1,5-diazabicyclo [4,3,0] -5-nonene were used as raw materials. Was performed to obtain 12.6 g of a viscous liquid (theoretical yield: 72.8%). Elemental analysis, ¹ H
From NMR, MS, etc., this viscous liquid is 1-methyl-
1-azonia-5-azabicyclo [4,3,0] -5
It was confirmed to be nonene methyl carbonate. (Second step) 1-methyl-1-azonia-5-azabicyclo [4,
The same operation as in Reference Example 1 was carried out except that 8.0 g of 3,0] -5-nonenemethyl carbonate and 4.3 g of maleic acid were used. As a result, 1-methyl-1-azonia-5-azabicyclo [4,3 , 0] -5-Nonene monomalate 8.
7 g (66.7% yield based on 1,5-diazabicyclo [4,3,0] -5-nonene) was obtained. According to the present invention, high purity mono-nitrogen-containing
An electrolyte for an electrolyte comprising a heterocyclic quaternary ammonium organic acid salt can be provided at low cost.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 209/20 C07C 209/20 209/68 209/68 211/63 211/63 (56) References JP-A-59-78522 JP, A) U.S. Pat. No. 4,377,692 (US, A) U.S. Pat. No. 2,635,100 (US, A) U.S. Pat. No. 4,410,863 (US, A) Italian patent 1,135,530 (IT, A) West German Patent Specification No. .1) (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 213/00 C07D 295/00 C07D 487/00

Claims (1)

(57) [Claims] Mono the corresponding nitrogen-containing heterocyclic tertiary amine is reacted with a carbonic acid diester - the first step and the nitrogen-containing heterocyclic quaternary ammonium carbonate, and the resulting mono - nitrogen-containing het
The second step, is manufactured through the Mono The filtrate ring quaternary ammonium carbonate is mixed with an organic acid anion-exchange organic acid corresponding by generating carbon dioxide - nitrogen-containing heterocyclic
An electrolyte for an electrolytic solution, comprising an organic acid salt of a cyclic quaternary ammonium. 2. Electrolyte for the electrolytic solution of claim 1, wherein the nitrogen-containing heterocyclic tertiary amine is a nitrogen-containing heterocyclic aliphatic amines. 3. Electrolyte for the electrolytic solution of claim 1, wherein the nitrogen-containing heterocyclic tertiary amine is a nitrogen-containing heterocyclic aromatic amine. 4. The electrolyte for an electrolytic solution according to any one of claims 1 to 3 , wherein the organic acid is a monocarboxylic acid. 5. The electrolyte for an electrolytic solution according to any one of claims 1 to 3 , wherein the organic acid is a dicarboxylic acid.